(Z)-5-(4-Fluoro­benzyl­idene)-1,3-thia­zolidine-2,4-dione

Abstract

In the title compound, C₁₀H₆FNO₂S, the benzene and thia­zolidine rings make a dihedral angle of 7.52 (3)°. Intra­molecular C—H⋯O and C—H⋯S hydrogen bonds result in the formation of nearly planar five- and six-membered rings; the adjacent rings are nearly coplanar. In the crystal structure, inter­molecular N—H⋯O hydrogen bonds link the mol­ecules.

Related literature

For general background, see: Barreca et al. (2002 ▶); Botti et al. (1996 ▶). For a related structure, see: Guo et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₀H₆FNO₂S

• M _r = 223.22

• Orthorhombic,

• a = 26.519 (5) Å

• b = 36.509 (7) Å

• c = 3.8490 (8) Å

• V = 3726.6 (13) ų

• Z = 16

• Mo Kα radiation

• μ = 0.34 mm⁻¹

• T = 294 (2) K

• 0.30 × 0.10 × 0.10 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.905, T _max = 0.967

• 2087 measured reflections

• 1059 independent reflections

• 790 reflections with I > 2σ(I)

• R _int = 0.042

• 3 standard reflections frequency: 120 min intensity decay: none

Refinement

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 0.121

• S = 1.04

• 1059 reflections

• 136 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.66 e Å⁻³

• Absolute structure: Flack (1983 ▶), no Friedel pairs

• Flack parameter: 0.0 (2)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Siemens, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O2i	0.86	1.98	2.830 (5)	171
C5—H5A⋯S	0.93	2.54	3.241 (5)	133
C7—H7A⋯O2	0.93	2.50	2.870 (5)	104

Symmetry code: (i) .

supplementary crystallographic information

Comment

Thiazolidines are an important class of heteroaromatic compounds and have widespread applications from pharmaceuticals (Barreca et al., 2002) to materials (Botti et al., 1996). As part of our ongoing studies in this area (Guo et al., 2006), we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···O and C—H···S hydrogen bonds (Table 1) result in the formations of nearly planar five- and six-membered rings; C (S/H5A/C4/C5/C7/C8) and D (O2/H7A/C7—C9). Rings A (C1—C6) and B (N/S/C8—C10) are, of course, planar and the dihedral angles between them are A/B = 7.52 (3)°, A/C = 4.73 (3)°, A/D = 6.90 (3)°, B/C = 3.63 (2)°, B/D = 2.39 (3)° and C/D = 4.56 (2)°. So, the adjacent rings are also nearly co-planar.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, thiazolidine-2,4-dione (10 mmol) and 4-fluorobenzaldehyde (10 mmol) were dissolved in ethanol (10 ml) in a round-bottomed flask (50 ml) and 5 drops of piperidine were added. The flask was heated in a modified domestic microwave oven at 300 W for 5 min. After cooling, the mixture was poured into water and the crude compound (I) filtered out. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C,N).

Figures

Fig. 1.

The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.

Crystal data

C10H6FNO2S	F000 = 1824
Mr = 223.22	Dx = 1.591 Mg m−3
Orthorhombic, Fdd2	Mo Kα radiation λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 25 reflections
a = 26.519 (5) Å	θ = 9–13º
b = 36.509 (7) Å	µ = 0.34 mm−1
c = 3.8490 (8) Å	T = 294 (2) K
V = 3726.6 (13) Å3	Block, colorles
Z = 16	0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.042
Radiation source: fine-focus sealed tube	θmax = 26.0º
Monochromator: graphite	θmin = 1.9º
T = 294(2) K	h = 0→32
ω/2θ scans	k = 0→44
Absorption correction: ψ scan(North et al., 1968)	l = −4→0
Tmin = 0.905, Tmax = 0.967	3 standard reflections
2087 measured reflections	every 120 min
1059 independent reflections	intensity decay: none
790 reflections with I > 2σ(I)

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053	w = 1/[σ2(Fo2) + (0.05P)2 + 3P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.121	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.38 e Å−3
1059 reflections	Δρmin = −0.66 e Å−3
136 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), no Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.0 (2)
Secondary atom site location: difference Fourier map

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S	0.08943 (4)	−0.00189 (3)	−0.0089 (5)	0.0379 (3)
F	−0.06109 (11)	0.13395 (8)	0.6207 (12)	0.0681 (12)
O1	0.13745 (13)	−0.05739 (9)	−0.3062 (14)	0.0619 (12)
O2	0.21942 (10)	0.03754 (8)	0.2142 (14)	0.0493 (10)
N	0.18501 (14)	−0.01228 (9)	−0.0627 (14)	0.0425 (11)
H0A	0.2136	−0.0219	−0.1150	0.051*
C1	−0.01787 (17)	0.11646 (12)	0.5430 (15)	0.0416 (12)
C2	0.02675 (18)	0.13443 (12)	0.5921 (16)	0.0484 (15)
H2A	0.0273	0.1584	0.6744	0.058*
C3	0.07078 (19)	0.11621 (11)	0.5166 (17)	0.0444 (13)
H3A	0.1015	0.1278	0.5559	0.053*
C4	0.07035 (16)	0.08082 (10)	0.3826 (13)	0.0346 (11)
C5	0.02378 (16)	0.06382 (12)	0.3314 (15)	0.0400 (12)
H5A	0.0225	0.0402	0.2421	0.048*
C6	−0.02016 (15)	0.08195 (12)	0.4125 (16)	0.0452 (14)
H6A	−0.0512	0.0707	0.3782	0.054*
C7	0.11827 (16)	0.06366 (11)	0.3095 (14)	0.0352 (10)
H7A	0.1462	0.0772	0.3782	0.042*
C8	0.12929 (15)	0.03151 (11)	0.1597 (14)	0.0317 (10)
C9	0.18224 (17)	0.02026 (11)	0.1107 (15)	0.0370 (12)
C10	0.14053 (17)	−0.02927 (12)	−0.1510 (17)	0.0450 (13)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S	0.0303 (5)	0.0391 (5)	0.0444 (6)	−0.0005 (4)	0.0015 (7)	−0.0028 (6)
F	0.0400 (16)	0.0705 (18)	0.094 (3)	0.0212 (14)	0.003 (2)	−0.024 (2)
O1	0.058 (2)	0.0465 (17)	0.081 (3)	0.0105 (16)	0.000 (3)	−0.026 (2)
O2	0.0267 (16)	0.0444 (16)	0.077 (3)	0.0002 (12)	−0.0039 (19)	0.001 (2)
N	0.0295 (18)	0.0403 (18)	0.058 (3)	0.0068 (15)	0.001 (2)	0.001 (2)
C1	0.033 (2)	0.051 (2)	0.041 (3)	0.012 (2)	0.003 (2)	−0.009 (3)
C2	0.047 (3)	0.042 (2)	0.056 (4)	0.012 (2)	−0.009 (3)	−0.018 (3)
C3	0.047 (3)	0.036 (2)	0.050 (3)	−0.0028 (19)	−0.002 (3)	−0.007 (3)
C4	0.031 (2)	0.036 (2)	0.036 (3)	0.0030 (17)	−0.002 (2)	−0.002 (2)
C5	0.035 (2)	0.038 (2)	0.047 (3)	0.0012 (17)	−0.001 (2)	−0.006 (2)
C6	0.0209 (18)	0.056 (3)	0.058 (4)	−0.0019 (18)	0.007 (2)	−0.018 (3)
C7	0.030 (2)	0.042 (2)	0.033 (3)	−0.0057 (17)	0.000 (2)	0.008 (2)
C8	0.024 (2)	0.040 (2)	0.031 (3)	0.0007 (16)	−0.003 (2)	0.009 (2)
C9	0.032 (2)	0.037 (2)	0.042 (3)	0.0039 (18)	−0.001 (2)	0.011 (2)
C10	0.038 (2)	0.042 (2)	0.055 (4)	0.0065 (19)	−0.002 (3)	0.002 (3)

Geometric parameters (Å, °)

S—C8	1.739 (4)	C2—H2A	0.9300
S—C10	1.770 (5)	C3—C4	1.391 (6)
F—C1	1.346 (5)	C3—H3A	0.9300
O1—C10	1.191 (6)	C4—C5	1.396 (6)
O2—C9	1.237 (5)	C4—C7	1.445 (6)
N—C9	1.364 (6)	C5—C6	1.376 (6)
N—C10	1.375 (6)	C5—H5A	0.9300
N—H0A	0.8600	C6—H6A	0.9300
C1—C6	1.358 (6)	C7—C8	1.340 (6)
C1—C2	1.366 (7)	C7—H7A	0.9300
C2—C3	1.375 (6)	C8—C9	1.475 (6)
C8—S—C10	92.6 (2)	C6—C5—H5A	119.9
C9—N—C10	117.9 (4)	C4—C5—H5A	119.9
C9—N—H0A	121.1	C1—C6—C5	119.5 (4)
C10—N—H0A	121.1	C1—C6—H6A	120.3
F—C1—C6	119.0 (4)	C5—C6—H6A	120.3
F—C1—C2	118.6 (4)	C8—C7—C4	131.0 (4)
C6—C1—C2	122.4 (4)	C8—C7—H7A	114.5
C1—C2—C3	118.3 (4)	C4—C7—H7A	114.5
C1—C2—H2A	120.9	C7—C8—C9	120.4 (4)
C3—C2—H2A	120.9	C7—C8—S	129.9 (3)
C2—C3—C4	121.4 (4)	C9—C8—S	109.6 (3)
C2—C3—H3A	119.3	O2—C9—N	124.0 (4)
C4—C3—H3A	119.3	O2—C9—C8	125.1 (4)
C3—C4—C5	118.2 (4)	N—C9—C8	110.9 (4)
C3—C4—C7	117.9 (4)	O1—C10—N	124.9 (4)
C5—C4—C7	123.9 (4)	O1—C10—S	126.1 (4)
C6—C5—C4	120.2 (4)	N—C10—S	109.0 (3)
F—C1—C2—C3	179.1 (5)	C4—C7—C8—S	0.6 (9)
C6—C1—C2—C3	−2.2 (9)	C10—S—C8—C7	177.2 (5)
C1—C2—C3—C4	2.1 (9)	C10—S—C8—C9	−1.5 (4)
C2—C3—C4—C5	−1.0 (8)	C10—N—C9—O2	177.5 (5)
C2—C3—C4—C7	179.8 (5)	C10—N—C9—C8	−1.9 (6)
C3—C4—C5—C6	0.0 (8)	C7—C8—C9—O2	3.9 (8)
C7—C4—C5—C6	179.1 (5)	S—C8—C9—O2	−177.2 (4)
F—C1—C6—C5	179.8 (5)	C7—C8—C9—N	−176.7 (4)
C2—C1—C6—C5	1.2 (9)	S—C8—C9—N	2.2 (5)
C4—C5—C6—C1	−0.1 (9)	C9—N—C10—O1	178.9 (6)
C3—C4—C7—C8	−174.7 (5)	C9—N—C10—S	0.7 (6)
C5—C4—C7—C8	6.3 (9)	C8—S—C10—O1	−177.6 (6)
C4—C7—C8—C9	179.3 (5)	C8—S—C10—N	0.6 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2i	0.86	1.98	2.830 (5)	171
C5—H5A···S	0.93	2.54	3.241 (5)	133
C7—H7A···O2	0.93	2.50	2.870 (5)	104

Symmetry codes: (i) −x+1/2, −y, z−1/2.